Corrosion inhibiting composition



Patented Oct. 28, 1952 Gerald David Galvin and. Alexander Espie McAulay,Fulham, England; assignors to Shell Development Company, San Francisco,Calif., acorporation of Delaware No Drawing. Application December21,1948, Se-

rial No. 66,593. In Great Britain March 12,

This invention relates to compositions havin the ability of displacingmoisture, corrosive materials and the like-from corrosive surfaces. Theinvention also pertains to the formation on such surfaces of anon-corrosive moisture resistant protective film. More particularly,this invention pertains to corrosion inhibiting compositions suitablefor protecting metal and non-metal surfaces by rendering them imperviousto water, electrolytic solutions, corrosive fluids, gases, and the like,by displacing said contaminant from said surfaces and forming thereon atenacious pro tective film. a

It is well known that moisture, corrosive fluids and gases, e. g. H28,S02, etc. readily attacknot only metallic surfaces .but non-metallicsurfaces,

and cause corrosion, rusting, pitting andother damage to such surfaces.Also, aqueous solutions when in contact with a metallic surface readilyattack it and cause corrosion and rusting.

Under certain conditions the problem of cone-- sion becomes exceedinglyserious because o ce started it becomes progressively accelerated. Thus,oils containing small amounts of water become very corrosive tocontactin metals. This is due to the fact that oils andparticularlyliquid petroleum hydrocarbons are very good solubilizers ofoxygen and any moisture present therein becomes surrounded by an almostinexhaustible store of oxygen. Moisture under such i conditions isinhibited from evaporating and since the rate of transfer of oxygen fromhydrocarbons, such as mineral oil or gasoline,'to water; is limited,ideal conditions for rusting and corrosion are set up. The presence ofelectrolytes and formation of corrosive decomposition products in oilsand the like also greatly increasethe rate of corrosivity.

Under conditions where, in addition to those" enumerated, elevatedtemperature is encountered, corrosion activity is greatly accelerated.Thus,

chinery and industrial equipment, readilyattack and rust or corrodecontacting metal surfaces.

Thedamage thus caused is not to the metal sur-- face alone for rustparticles frequently break off is Qlaims. (c1. loa 4) andferiter thecirculating system of engines, and I cause pluggingclogg'ing and foulingof conduit lines, columns, plates, and lines of cracking equipment tilbes evaporators, etc.

Corrosion of alloyed bearings and other alloyed surfacesldue tocontactwith water can attain such an aggravated state as to cause great fatiguestressesto be set up, which ultimately resuit in cracking of'the metal.I

, Thepro'ble n is equally serious when combating rusting and corrosionofstee1 drums, storage tanksused to store gasoline, hydrocarbon oils andthe dike. Moisture adhering to pickled steel, quenched steel, equipmentsuch as instrumentsi engine starters and generators on landing crafts,

hydraulic systems, machinery for metal processing and the like are alsoextremely susceptible to corrosion and must be protected.

Besides metal surfaces, materials such as rub ber equipment, electricalinsulation, brake andclutch lining, etc. suffer damage when in contactwith water, aqueous solutions, corrosive .fluids and the like.

. Such contaminants 'also have a detrimental effect upon the medium inwhich they are dispersed. In lubricating and liquid fuel mediums,

they cause oxidation, interfere with the functioning of additives ordecrease their efficiency, form emulsions and thickening of the fluidand gengrally cause gumming and sticking of movable pars.

Countless materials and compositions have been tried for protectingsurfaces such as metal surfaces against damage caused by water,corrosive. fluids and the like by forming on said sur face anon-reactive corrosion preventive film.

Metal surfaces have been coated or treated with.

protective film. It is another object of this in-- vention to protectmetallic surf-aces with a waterdisplacing, water-resistant non-corrosiveprotecpersing media are preferably derived from petroleum hydrocarbonsand may include various petroleum naphtha cuts, mineral spirits, mineralseal oil, kerosene, gas oils, kerosene SOz-extract, aromatic solvents,petroleum ether, aromatic hydrocarbons, such as benzene, p-xylene,o-Xylene, cumene, butyl benzene; paraifinic hydrocarbons, e. g. normalhexane, dimethyl pentane, octane, nonane, undecane, dodecane;cycloparamns, e. g. cyclohexane, methylcyclohexanejisopropylcyclohexane; halogenated hydrocarbons such as chlorinatedkerosene, carbon tetrachloride,

-' .I-chloroform, etc.

tive film having no detrimental efiect upon the metal surface treated.It is'still another object of this invention to provide metal surfaceswith'a water and acid-resistant film which is not susceptible to ruptureeven at elevated temperatures and which could be readily removed-whendesired. Still another object of this invention is to form protectivefilms on metal surfaces which are not detrimental to, contacting fluidsand which do not interfere with their function as lubricants, fuels,hydraulic fluids, quenching agents and the like. Another object of thisinvention is'to form a composition of matter capable of protecting metalsurfaces from corrosion, said composition also possessing lubricatingproperties. I Another object is to form film-forming' metal-protectivecompositions which are stable and readily miscible with petroleumhydrocarbon s, such as lubricating oils and the like. It is also anotherobject of this invention to treat surfaces whether metallic ornon-metallic, so as to formthereon a protective film which is imperviousto moisture and" corrosive fluids, and which can be' readily removedwhen desired. Other objects will be apparent from the followingdescription.

It has now been discovered that various metals and other materialssubjected to corrosive influences can be protected simply andeffectively by treatment with a composition of matter comprising a majoramount of a light petroleum hydrocarbon and mixtures thereof having aboiling range of from 50 C. to about 370 C. and minor, but critical,amounts of a) "a particular petroleum refineryby-product which willhereinbelow be fully discussed and identified, (b) a specific type ofmetal protective agent or agents, (0) an oil-soluble petroleum sulfonatederived from theraffinate fraction of'a solvent treatedpe troleumhydrocarbon rich in aromatics, said sulfonates having water displacingproperties, and

tension'and penetrating properties both towards the metal an'd' occludedimpurities present so as t'o'allo'w-the'metal protective agent to get tothe surface, displace any impurity thereon and help form a protectivefilm. These carriers or disnon-corrosive, surface pro- The petroleumrefinery by-products referred to hereinbefore andwhich constitute one ofthe chief additive agents of compositions of this invention are known inrefinery terminology as petroleum residues or lubricating still bottoms.Substantial amounts of these petroleum residues are obtained during theprocessing of various petroleum crudes and particularly those rich innatural acids such as the cyclic acids and more specifically thenaphthenic acids. These constituents along with resinous bodies andother impurities which are generally present in Venezuelan, Trinidad,Californian, Borneo and Roumanian crudes must be removed in order toavoid the formation of emulsions during the working up process intherefining of the crude to high grade-lubricants.

The general procedure for removing these materials in order to obtain ahigh grade lubricant is to subject the crude to a distillationtreatmentin the presence of alkaline substances such as caustic soda,caustic potash, lime, the alkaline earth hydroxides, carbonates, such ascalcium,

barium and magnesium oxide, hydroxideor the carbonates andtheir-mixtures'and the like. 1 The acidic constituents present in thecrude remain v behind as a residue'during this distillation treatment inthe form of soaps together with resinous materials, asphalt-likepolymerization products, some high-boiling viscous mineral oil and othermaterials. 9

These petroleum residues have little valueimpractical to recover themfrom the residue and therefore the residue generally is considered awaste by-product and is generally discarded as such or is occasionallyused asasource of fuel.

It has now peen found'that these petroleum residues when ad'miXed'withcertain protective agents, petroleum sulfonates and spreading agents andsaid additives are dispersed togetherin a light petroleum hydrocarbonfraction, an out-:-

st'anding water displacing composition .having excellent corrosionpreventive'properties can be obtainedfi Additionally by the presenceofsaid petroleum residues the amount of the other additives comprising"compositions of this'invention can be reduced to a minimum. 7

The preferred petroleum residuesfallingwithin the scope of thisinvention are those obtained by'the redistillation of a lubricating oildistillate containing 'organic] cyclic" acids suchas naphthenic acids,which ha've been treated with lime. However; other alkaline earth oxidessuch as-barium oxide or magnesium oxide or their hydroxides and/orcarbonates may be employed in 'th e preparation'of these petroleumresidues."

Thus, as aspecific example, a desired petroleum residue may be-obtainedin the distillation" of lubricating oil from a California base oil andlime exceptional wetting power when in combination with theabove-mentioned petroleum residues so as to be capable of displacingmoisture and other contaminants from various surfaces and thereby aid orallow the protective agent to come in direct contactwith the surfacebeing protected areoilsoluble sulfonates' derived from rafiinatefractions of solvent-treated petroleum oils. The petroleumfractionsiwhich may 'beysolvent-treated prior to sulfonation may.include petroleum, naphthas, kerosene-gas oils, transformer oils,turbine oils, lubricating oils-and j the like. includessulfur dioxide,phenol, furfural, nitrobenzene, Chlorex, which is the trade nameforB,B-dichloroethyl ether, etc. The raflinate fraction or layer isthenremoved and is sulfonated with a suitablesulfonating. agent, such,as'sule, furic acid of desired concentration, oleum, SO2SO3mixtures,chlorosulfonic acid and the like. The sludge which is formed isremoved and the sulfonic acids remaining. in the sour oil are recoveredby any suitable means such as by alcoholic extraction and thereafterneutralized.

with-metal or organic basecompounds such as alkali, alkaline earth andheavy metal compounds or amines, quaternary ammonium compounds and thelike. Instead of recovering the sulfonic acids from the sour oil andthen neutralizing,

them, the sulfonic acids may be neutralized when in the oil and thenrecovered, or the entire oilcontaining the neutralized sulfonates may.be used. Oil-solublealkali and alkaline earth petroleum sulphonatesobtained from rafiinate fractions of solvent-treated light petroleumfractions waxes, alkali and alkaline earth metal salts, e. g.

sodium, potassium, calcium or magnesium salts of wool grease, oleicacid, stearic acid, petroleum acids, naphthenic acids, alkali salts ofsulfated alcohols having between about 8 and about 20 carbon atoms inthe molecule, e. g. sodium oleyl sulfate, sodium lauryl sulfate, sodiumocenol sulfate, ammonium lauryl sulfate, neutralized alkylated aromaticsulfonates, and alkali salts of mono and poly alkyl esters ofsulfodicarboxylic The solvents may of solvent-treated, low-boiling,petroleumhydroscarbons, when used alone or in combination with otherwetting agents referred to above, possess; the unique property ofdisplacing moisture from. metal surfaces and in addition act as powerfulpenetrants, which however are readily displaceable by the protectivefilm-forming agent of this invention. This is apparently. :due tov thefact that these wetting agents are-substantially miscible with and havea great affinity. for water enabling them to remove moisture from themetal surfaceand allowing the penetrant andiprotectivefilm-formi'ngagent to come in direct contact with the surface being treated.-.

The protective film-forming, water dis placing material of thisinvention is a fatty material,

preferably a partially hygroscopic fatty material such as refined woolfat or lanolin. This material is obtained by extraction, preferablyunde'ri inert conditions, of rawv wool withrvolatilesolvents, such asnaphtha, benzol, carbon disulfide, or by scouring the wool with soapsolutions and then acidifying with sulfuric acid. Soaps and. free acidsare .removed .from the fatand the fat'is from metallic surfacesandforming thereon a tenacious protective film. vJust how lanolinperforms this function is not exactly understood,

. but it is believed that the alcohols present therein '(cholesterins)have a strong v affiity. for water while the ester component ofthe' fathave" astrong affinity for-the metal and forms :the'protectivefilm'thereon. Instead of refined wool fat, the product ingits crude formor simply neutralized with alkali or alkaline earth metal oxide,hydroxide .orcarbonatemay befused.

In orderto aid the .ianolinin forminga more tenacious and-permanentfilm'as well as to increase its oiliness and lubrica'ting properties,.oleaginous' materials can be-added. Additives which can be used forthis'purpose are heavy waxes such as carnauba wax, can'dellila wax,Japan wax, animal waxes, e. g. spermaceti, sperm oil, insect waxes, e.g. beeswax, Chinese insect wax and synthetic --w'axe s, can Abe used; or

acid, e. g. sodium saltof diamylsulfosuccinic I acid, sodium salt ofdilauryl sulfosuccinic acid, disodium'monocetyl monosulfosuccinate, etc.

The wetting agents of this invention, namely oil-solublesulfonates'derived from the rafiinates asphaltic bitumens' and 'blowns-emrdrying oils,- such as blownsrapese'ed oil. Also,-polyhydricalcohol-fatty acid esters such as glycerol mono oleate, glycerolmonostearate, pentaerythritol mono and dioleate and stearate, and thelike can. be used.

To aid in spreading the film formingrnetaf protective agent evenly,minor amounts of alcohols and more particularly the branched chainalcohols, keto alcohols and cycloalkanols having between about 5 to 19'carbon atoms in the molecule and preferably between. about 6 to'8 carbonatoms, inclusive, are added to compositions of this invention. Ketoalcohols andlcyclic alcohols are preferred and includediacetone alcohol,

4-tertiaryamylcyclohexanol, ditertiaryamyltzyclohexanol,methylcyclohexanol and the like. Branched-chain alcohols which can beused can be derived from alcohols containing 5 to 19 carbons orsuchalcohqls as p -tertiaryamylphenoxyethanolandditertiaryamylphenoxyethanol and the like. .Thealcohols need not beused-in amounts above 10% by weightand usually are not added in excessof 5% by weight; The alcohols function as spreading agents. Thus oncethe wetting agent with the aid of the penetrant succeeds in getting tothe surface and removing moisture or other contaminant, the alcoholhelps spread uniformly the film-forming protective agent onto thetreated surface.

All. ingredients which constitute the present composition must bepresent at all times. The

absence of any one ingredient reduces the overall,

elficiency of the composition to such a degree as to render it almostuseless as a moisture displacing corrosion inhibiting composition. Y

Compositions of this invention may be rormulated as follows:

' Amount (per cent weight), Petroleum residues as defined 1511035Protective agents, e. g. lanolin, blown rapeseed oil, waxes, asphalticbitumen and their mixtures 2 to Wetting agents, e. g. petroleumsulionates derived from solvent-treated rafimate oil fraction. 1 to 1.0Spreading agent, e. g. alcohols l to 10 Light hydrocarbon boilingbetween 50 and 370 C. Balance The following examples arev given by wayof illustrating compositions of this invention, all parts being parts byweight.

EXAMPLE I mixture heated at about 50 C. until a homogeneous mass wasobtained. The mixture was allowed to cool and then about 2 parts ofchase-- tone alcohol, 10 parts of special boiling point spirit (boilingpoint 100 to 160 C.) and about 30 parts of white spirit (boiling point140 to 160 C.) were added. The composition thus .formed pos sesscdexcellent water displacing-and anti-corrosion properties. 1

EXAIWPLEYH The following table gives other compositions of thisinvention which may beprepared by th method set out in the aboveexample:

ing properties compositions of this invention pos V sess, the followingtests were made:

Two metal strips were cleaned and one metal strip was coated withcomposition of Example: I

and the other metal strip was coated with a. commercial composition Xknown to contain lanolin and sodium petroleum sulfonate. The twometalstrips were then subjected to outdoor'weathering and. signs of rusting,cracking or reticulation Although the essential ingredients whichconstitute compositions of this invention must be present, otheradditives can be included such aslinear polymer thickeners, asphalts,pour point depressants, dyes, alkyl and alkylol amines, organic acids,e. g. cresylic acid and naphthenic acid, phenolic compounds and thelike- The addition of such additives is particularly desired whencompositions of this invention are required to be used as temporarylubricants.

The present compositions may be applied to a surface to be protected bya means such. as immersing, flooding, spraying, brushing, troweling andthe like. The protective film formed on said surfaces adherestenaciously enough to withstand handling, light polishing movement andhigh temperatures for long periods of time. It can be removed whendesired by a suitable solvent or by simply rubbing with a cloth.

.The present invention having thus been fully described is not to belimited by any specific examples which have been presented herein solelyfor the purpose of illustration, but only by th following claims. I

We claim as our invention:

1 Acomposition for displacing moisture and preventing corrosion ofmetals having the following formula and proportions by Weight:

, Per cent Limed petroleum residue rich in natural cyclic acids 20Lanolin Q 10 Sodium salt of oil-soluble petroleum sulfonic acid derivedfrom raffmate fraction of a solvent-treated oil .3

Zinc naphthenate 5 Diacetone alcohol 2- White spirits Balance (a) Limedpetroleum residue Barium petroleum res1due Magnesium petroleum rcs1dueLanolin Blown rapeseed oil Hydrocarbon residue from cra parafiiuwax Nasalt of oil-soluble naphtha suliomc aci Ca salt of oil-soluble petroleumsulfonic acid (both acids obtained irom oil raffinate traction) (d)Diacetone alcohol Cyclohexanol (e) Light hydrocarbon boiling from 50 to370 C. and mixtures thereof The amounts of each additiveused may varywithin the scope as set forth hereinbefore'.

To illustrate the pronounced corrosion inhibit- 2. A composition fordisplacing moisture and preventing corrosion of metals having thefollowing formula and proportions by Weight:

1 ingof aliphatic and cycloaliphatic al- Per cent 15 to 35 2 to 15 lto "'cohols Light petroleum hydrocarbon boiling be-' V tween 50"- and 370 C;.Balance 'BJIA composition fordisplacirig moisture and preventingcorrosion of metal surfaces comprising a major amount of white spirits,between and 35% of. alkaline earth metal salt of petroleum residues richin natural cyclic acids, between 1% and 10% of alkali metal salt ofoilsoluble petroleum sulfonic acid, between 1% and 10% of an aliphaticalcohol and between 2% and 15% of lanolin, all percentages being byweight.

4. A composition for. displacing moisture and preventing corrosion ofmetal surfaces comprising a major amount of white spirits, between 15%and 35% of alkaline earth metal salt of petroleum residues rich innatural cyclic acids, between 1% and 10% of alkali metal salt ofoil-soluble petroleum sulfonic acid, between 1% and 10% of an aliphaticalcohol and between 2% and 15% of neutralized wool fat, all percentagesbeing by weight.

5. A composition for displacing moisture and preventing corrosion ofmetal surfaces comprising a major amount of White spirits, between 15%and 35% of alkaline earth metal salt of petroleum residues rich innatural cyclic acids, between 1% and 10% of alkali metal salt of oilsoluble petroleum sulfonic acid, between 1% and 10% of an aliphaticalcohol and between 2% and 15% of blown rapeseed oil, all percentagesbeing by weight. w

6. A composition for displacing moisture and preventing corrosion ofmetal surfaces comprising a major amount of kerosene, between 15% and35% of alkaline earth metal salt of petroleum residues rich in naturalcyclic acids, between 1%- and 10% of alkali metal salt'of oil-solublepetroleum sulfonic acid, between 1% and 10% of an aliphatic alcohol andbetween 2% and 15% of lanolin, all percentages being .by weight.

7. A composition for displacing moisture and preventing corrosion ofmetal surfaces comprising a major amount of kerosene, between 15% and35% of alkaline earth metal salt of petroleum residues rich in naturalcyclic acids, between 1% and 10% of alkali metal salt of oil-solublepetroleum sulfonic acid, between 1% and 10% of an aliphatic alcohol andbetween 2% and 15% of neutralized wool fat, all percentages being byweight.

'8. A composition for displacing moisture and preventing corrosion ofmetal surfaces compris- I between 1% and 10% of' alkali metal salt-ofioilsoluble petroleum sulfon'ic acid, between '%and 10 diacetone alcoholand btWllZ lanolin, all percentages 'being'byweight:

- 10. A composition for displacing-moisture'and "preventing corrosion'of metal surfaces comprislld 15% i'ng a'majdr' amount ofwhitespiritsfbetween 15% and 35% of alkaline'earth metal salt-ofpetroand 35% of alkaline earth metal salt of petroleumresidues rich innatural cyclic acids, between 1% and 10% of an oil-soluble alkali metalpetroleum sulfonate, between 1% and 10% of an aliphatic alcohol andbetween 2% and 15% of a fatty material selected from the groupconsisting of fatty oil and esters of high molecular weight fatty acids,all percentages being by weight.

12. An anti-corrosion composition comprising a major amount of a lightpetroleum hydrocarbon having a boiling point not exceeding about 370 C.,between 15% and 35% by weight of a metal salt of petroleum residues richin natural cyclic acids, between 1% and 10% by'weight each of anoil-soluble sulfonate and an alcohol selected from the group consistingof aliphatic and cycloaliphatic alcohols and between 2% and 15% byweight of a fatty materialselected from the group consisting of fattyoil and esters of high molecular weight fatty acids.

phatic alcohols and between 2% and 15% by weight of a fatty materialselected from the group consisting of fatty oil and esters of highmolecular weight fatty acids.

14. An anti-corrosion composition comprising a major amount of alightpetroleum hydrocarbon having a boiling point not exceeding about 370 0.,between 15% and 35% by weight of a metal salt of a petroleum residuerich in natural cyclic acids, between 1% and 10% by weight each of anoil-soluble sulfonate and a cycloaliphatic alcohol containing 5 to 19;carbon atoms in the molecule and between 2% and 15% by weight of a fattymaterial selected from the the group consisting of a fatty oil and anester of a high molecular weight fatty acid.

15. An anti-corrosion composition comprising a major amount of a lightpetroleum hydrocarbon having a boiling point not exceeding about 370 0.,between 15% and 35% by weight of a metal salt of a petroleum residuerich in natural cyclic acids, between 1% and 10% by weight each of anoil-soluble sulfonate and an aliphatic a1- cohol containing 5 to 19carbon atoms in the 16. An anti rust composition comprising a ma- 11 12jor' amount of a, light liquid petroleum hydrocer- REFERENCES CITED honand mmor amaunts each of the 'ml'lowmg The following references are ofrecord in the materials: between 15 and 35% by weight of a m of thisatent: metal salt of petroleum residues rich in natural 8 p cyclic acidsbetween 1% and 10% by weight 5 UNITED STATES PATENTS each of anoil-soluble sulfonate, and an alco- Number Name Date 1101 selected fromthe group consisting of .ali- 92,924 Wyckoff July 20, 1867 phatic and-;cyc10alipha.tic alcohols, and between 158,095 Lee Dec. 22,1874 2 and15% by weight of a, fatty material se- 2,182,992 Lebo Dec. 12,1939lected from the group consisting of fatty oil 10 2,373,787 .Sharp Apr.17,1945 and esters of high molecular weight fatty acids. 2,392,102Ruedrich Jan. 1, 1946 2,402,793 White et a1 M. Home 25, 1946 G RA D AVVI 2,450,321 White Sept. 23, 1948 ALEXANDER ESPIE MCAULAY. 2,509,786:Schiermeier Miiy 30, ,19 50

1. A COMPOSITION FOR DISPLACING MOISTURE AND PREVENTING CORROSION OFMETALS HAVING THE FOLLOWING FORMULA AND PROPORTIONS BY WEIGHT: LIMEDPETROLEUM RESIDUE RICH IN NATURAL CYCLIC SODIUM SALT OF OIL-SOLUBLEPETROLEUM SULFONIC ACID DERIVED FROM RAFFINATE FRACTION OF A